Oil soluble anionic surface active agent

ABSTRACT

An oil soluble anionic surface active agent consisting essentially of at least one member selected from the group consisting of a sulfonic acid, a sulfonate, and mixtures thereof, of an aliphatic monoolefin having a carbon atom number in the range of 32-40 and expressed by the general formula   (WHEREIN, R is a saturated alkyl radical; R&#39;&#39;, R&#39;&#39;&#39;&#39; and R&#39;&#39;&#39;&#39;&#39;&#39; are each respectively a member selected from the group consisting of hydrogen and a saturated alkyl radical, providing that said R&#39;&#39;, R&#39;&#39;&#39;&#39; and R&#39;&#39;&#39;&#39;&#39;&#39; should not all be hydrogen and the total number of carbon atoms of said R, R&#39;&#39;, R&#39;&#39;&#39;&#39; and R&#39;&#39;&#39;&#39;&#39;&#39; is in the range of 3038).

United States Patent [191 Nagayama et al.

[451 May 13, 1975 OIL SOLUBLE ANIONIC SURFACE ACTIVE AGENT [73]Assignee: Lion Fat & Oil Co., Ltd., Tokyo,

Japan [22] Filed: Dec. 8, 1972 [21] Appl. No.: 313,427

Related US. Application Data [63] Continuation-impart of Ser. No.51,323, June 30,

1970, abandoned.

[52] US. Cl 260/513 R; 260/429.9; 260/448; 260/327; 260/501.19;260/501.21; 252/554; 252/8.7 [51] Int. Cl. C07c 143/02 [58] Field ofSearch 260/513 R, 429.9, 448, 260/501.21, 501.19

[56] References Cited UNITED STATES PATENTS 3,409,637 11/1968 Eccles eta] 260/513 3,424,694 1/1969 Stein et a] 260/513 3,487,104 12/1969 Dimondet al.,'.. 260/513 3,502,716 3/1970 Kite 260/513 3,531,518 9/1970 Ohrenet a1 260/513 FOREIGN PATENTS OR APPLICATIONS 1,072,601 6/1967 UnitedKingdom 260/513 R OTHER PUBLICATIONS Chemical Abstract, Vol. 65, p.10813 (1966).

Primary ExaminerLeon Zitver Assistant ExaminerNicky Chan Attorney,Agent, or FirmWoodhams, Blanchard and Flynn [57] ABSTRACT An oil solubleanionic surface active agent consisting essentially of at least onemember selected from the group consisting of a sulfonic acid, asulfonate, and mixtures thereof, of an aliphatic monoolefin having acarbon atom number in the range of 32-40 and expressed by the generalformula R I R' R" RIII (wherein, R is a saturated alkyl radical; R, Rand R' are each respectively a member selected from the group consistingof hydrogen and a saturated alkyl radical, providing that said R, R" andR" should not all be hydrogen and the total number of carbon atoms ofsaid R, R, R" and R is in the range of 30-38).

2 Claims, No Drawings OIL SOLUBLE ANIONIC SURFACE ACTIVE AGENT CROSSREFERENCE TO RELATED APPLICATION This application is acontinuation-in-part of Ser. No. 51 323, filed June 30, I970, nowabandoned.

BACKGROUND OF THE INVENTION a. Field of the invention The presentinvention relates to an oil soluble surface active agent which comprisessubstantially a sulfonic acid or sulfonate of a specific aliphaticmonoolefin as an active component thereof.

b. Description of the prior art As the oil soluble sulfonic-acid typesurface active agents produced from petroleum material in the prior art,such substances as, for instance, the salt of mahogany acid,alkylbenzene sulfonate, etc. are known, and these surface active agentshave been widely used as a dry cleaning detergent, an emulsifier, adispersant, a lubricant additive, a corrosion inhibitor and as a generalcleaning agent.

Among the foregoing substances, the mahogany acid salt consistssubstantially of alkylaryl sulfonate and it can be obtained as abyproduct on the occasion of the sulfuric acid refining of petroleum,but, because it is a substance originating from various hydrocarbons ofunknown constitution and containing therein many impurities so as torender its color tone inferior, it must be refined by treatment withactive clay or the like.

Accordingly, the qualities of the resultant product, per se, arevariable, and particularly when said product is to be used as oneconstituent of a high quality emulsifier composition, dry cleaningdetergent composition, etc., the mixing proportions of other compoundingingredients should be modified on account of the lack of uniformity ofsaid mahogany acid salt produced.

Further, as a disadvantage ascribable to the substance from which itoriginates, said salt of mahogany acid contains so large a quantity ofunsulfonated substances that an express treatment of deoiling byremoving the unreacted oil must be carried out in order to increase themahogany acid salt content thereof, thus increasing the production cost.The conventional commercial manufactures contain mahogany acid salt tothe extent of 60-70 percent, and the existence of a relatively largequantity of non-sulfonic acid salt contained therein constitutes a causeof the lack of uniformity in the products of the prior art.

Moreover, the handling of this mahogany acid salt is quite troublesomebecause of its high viscosity, and, as a matter of fact, it hasheretofore been customary to soften it by heating.

The alkylaryl sulfonate which has an alkyl radical of C is free fromsuch defects as discussed above, but its viscosity is as high as that ofthe foregoing mahogany acid salt so that the handling thereof istroublesome also.

And, in case of the long-chain alkylaryl sulfonate such as disclosed inthe US. Pat. No. 3,410,925, the process of application is rathercomplicated because the preparation of the hydrocarbon to be employed asthe material therefor requires further processing, namely, dimerizationand alkylation of the alkyl radical.

From the viewpoint of efficiency, per se, these oilsoluble surfaceactive agents in the prior art, because of the existence of cyclicaromatic compounds contained in molecules thereof, are considerablydifferent from the olefin sulfonic acid or its salt constituting theprincipal component of the surface active agent of the presentinvention, not to mention the difference of their solubility insolvents. They are also inferior to the compounds of the presentinvention in their.lubricative property, corrosion inhibiting property,emulsifying property, etc.

SUMMARY OF THE INVENTION The object of the present invention is toprovide a novel high-molecular, oil-soluble surface active agent whichcan remedy the aforementioned shortcomings of the prior art, and moreparticularly, an oil-soluble anionic surface active agent consistingessentially of at least one member selected from the group consisting ofa sulfonic acid, sulfonate (salt), and mixtures thereof, of an aliphaticmonoolefin having a number of carbon atoms in the range of 32-40 andexpressed by the general formula (wherein, R is a saturated alkylradical having either a straight chain structure or a branched-chainstructure; R, R", and R' are respectively either hydrogen or a saturatedalkyl radical having either a straight chain structure or abranched-chain structure, providing that said R, R" and R' should notall be hydrogen and the total number of carbon atoms of said R, R, R andR is in the range of 30-38).

As the material for use in present invention, a monoolefin of C -Cobtained by oligomerizing either monoolefins other than a-olefin orequivalent low molecular monoolefins into dimers, trimers and so on areapplicable.

As for the former monoolefin, either one with a branchedchain structureor one with a straight chain structure will do, but, preferably, amonoolefin of straight chain structure is particularly suitable.

In case of the latter monoolefin as the oligomerized material, in likefashion, either a branched-chain structure or a straight chain structurewill do, but, more preferably, a straight-chain a-olefin is applicable.

The latter material can be obtained at a high yield by, for instance, incase of dimerization, a reaction either between olefins of C -C orbetween a monoolefin of C -C and a monoolefin of C or more in thepresence of a catalyst.

In addition, the oligomer of olefin of C -C and preferably olefin of C Cconstitute important materials for the purpose of the present invention.

The former material, namely, monoolefin of C -C can be prepared by meanssuch as paraffin cracking, ethylene polymerization, elimination ofhydrogen chloride from chlorinated paraffin, dehydrogenation ofparaffin, etc., and the latter material for oligomerized olefin can alsobe prepared by the foregoing method.

As the catalyst for use in said oligomerization, organic metal compoundssuch as organic aluminum compounds, metallic oxides, alkali metallicsalts, boron fluoride, etc., are suitable.

Accordingly, the constitution of the oligomerized material varies withthe composition, the properties or the conditions of polymerization(such as temperature, time, pressure, etc.) of the lower molecularweight straight-chain olefin employed therefor. For instance, whendimerization is effected by employing a straightchain oz-olefin of G -Cthere are obtained high molecular monoolefins mainly having thebelowmentioned formulas or mixtures thereof.

41H, R CH CH CHCH CH=CHR (ii) 1.1 1

TH CH2 R cH cH cH CHCH=CHR1 (iii) R cH cH cH cH cH=cHR (iv) CH3 R CHJHCH CH=CH-R c ca f I (vi) R cH CH (CH2) n c C 3 (vii) R CH CH C CH(wherein, R is an alkyl radical having a carbon-chain length such thatthe total number of carbon atoms of each molecule is in the range of32-40.)

On this occasion, however, inasmuch there occurs the isomerization ofthe material, per se, prior to the dimerization, according to the kindof the catalyst employed, it is presumed that these compounds of saidformulas (i) and (ii) can be produced to a much greater extent thanthose of said formulas (iii) and (iv), and, moreover, furthercomplicated formulas are feasible from the viewpoint of the transitionpoint for the double bonding as well as the ways of combination of alkylchain lengths. Further, as for the trimer or the tetramer, there can beobtained other various formulas in addition to those mentioned above.But, it boils down to this: it suffices if the high molecularmonoolefins applicable to the present invention possess a carbon atomnumber in the range of 32-40 as expressed by the foregoing generalformula. Many of such monoolefins, because of their having a branchedchain or having a double bond inside thereof, even in case of astraight-chain mono-inner-olefin of the formula (iii) in the foregoing,show a low cloud point as well as pour point as compared with astraight-chain a-olefin having the same number of carbon atoms, anddespite the high molecular weight thereof, display such an unexpectedcharac- No. of carbon Cloud point Pour point atoms (C) (C) dimer olefin32 l l dimer olefin 36 5 2 The product according to the presentinvention is prepared by sulfonating the above-mentioned materials. Thesulfonated product thus obtained is serviceable as it is, but it ispreferably neutralized once and then employed either in that conditionwithout subjecting to hydrolysis or after subjecting it to hydrolysis.Also, a sultone ring opening agent can be added to the sulfonationproduct. The methods of sulfonation, neutralization and cracking ofsultone to be applied on this occasion are the same as that for theconventional watersoluble olefin sulfonate (for instance, the onesdisclosed in British Pat. Nos. 1,072,601 and 1,139,158). In other words,the product of the present invention can be obtained through a processin which: the feed material olefin in the form of a thin film iscontacted continuously with gaseous sulfur trioxide; then, the re actionproduct is further subjected to neutralization; subsequently, thesultones contained therein are subjected to ring-opening either by meansof hydrolysis or causing them to react with a sultone cracking agent.

As to the sulfonation processing, inasmuch as the feed material olefinhas the form of a liquid at room temperature by nature, it can be fedat, room tempera- (wherein n=0-2l) ture and independently as it is,without taking such troubles as an express heating or joint use of anysolvent. As for the sulfonation equipment, a continuous falling filmreactor is applicable, providing that it is so devised as to be capableof bringing a thin-film material into contact with S0 gas. In thiscontext, as to the applicable size, length, etc. of said equipment,there is no particular limitation thereof, but it ranges from alaboratory-size one to an industrial-size one. In short, a reactionapparatus suitable for preparing the product according to the presentinvention is a continuous sulfonator capable of performing a high degreeof sulfonation. The sulfonator of this sort is preferably provided withas large a heat exchangeable surface area as possible. In thisconnection, such a sulfonator which is provided therein with a thermalmedium capable of controlling the inner temperature thereof is of coursealso applicable to the present invention. Further, it is alsopracticable to employ a sulfonator having annexed thereto a post-reactorfor the purpose of completing the reaction.

As to the sulfonating agent to be employed in effecting the sulfonatingreaction, either of sulfur trioxide prepared through the oxidation ofsulfur dioxide and sulfuric anhydride stabilized liquid sulfur trioxideare applicable. The suitable concentration of gas for use in the reactoris in the range of ll percent by volume with the balance being an inertgas. As for the inert gas, it is usual to employ air, but it will alsodo to use nitrogen, carbon dioxide, sulfur dioxide gas, etc. in lieu ofair. The temperature of S0 gas being fed is in the range of 30-l0OC, andpreferably in the range of 4050C. The mol ratio of 50;, gas to the feedmaterial olefin is in the range of 0.5-1.5, and preferably in the rangeof 0.81.3. Furthermore, the preparation of mahogany acid salt accordingto the prior art is apt to be accompanied by the trouble that, shouldthe rate of conversion of the petroleum fraction to sulfonate be raisedtoo much, there will result an abrupt increase in viscosity to make theafter-treatment rather complicated, but for the product of the presentinvention, even when said conversion rate exceeds 90 percent, thereoccurs no such increase in viscosity as to make the handling thereofdifficult, and this also is an advantageous feature of the presentinvention. Next, as to the temperature for the sulfonation reaction,inasmuch as the feed material olefin has a low viscosity despite itshigh molecular weight as discussed in the foregoing, it can besulfonated without applying a high temperature, and, for instance, evenin case of a mixture of dimer olefin having 36 carbon atoms, it is wellsulfonated at a temperature of 50C or thereabout, and not only that, theresulting sulfonic acid mixture does not harden at a temperature above40C, either, and has a low viscosity, so that the sulfonation reactioncan be easily effected. The suitable reaction temperature is to behigher than the solidifying point of the feed material olefin by C ormore, but not exceeding 100C, and preferably in the range of 3070Chigher than said solidifying point.

The thus obtained sulfonated substance (acid) usually comprises at least30 percent of monoalkene sulfonic acid having a high molecular weight,0-50 percent of hydroxymonoalkane sulfonic acid, 0-30 percent of diandpoly-sulfonic acid, at least percent of l, 3- and 1, 4- sultones and thelike, and 0-60 percent of unreacted substances.

The neutralization of these mixtures is effected by adding thereto analkali metal hydroxide such as LiOI-I, NaOH, KOH, etc., carbonates suchas Na CO (NI-I CO etc., NH OI-I, organic amines (namely, primary,secondary and tertiary amines, alkanolamine, etc.) at the rate of 0.61.0 by equivalent per the introduced amount of $0 (in mol). And, thepreparation of the metallic salt of olefin sulfonic acid according tothe present invention can be also performed by subjecting theaforementioned mixture to hydrocracking by means of adding thereto analkaline earth metal hydroxide and the like such as that of Ca, Mg, Ba,Zn, Al, or subjecting the same to hydrolysis by adding thereto alkalimetal hydroxide and thereafter effecting double decomposition. Thealkaline earth of other metal salt for use in the present invention,such as the salt of Ca, Mg, Ba, Zn, Al, etc., can thus be prepared asabove.

Meanwhile, the sultones contained in the foregoing mixture producehydroxyalkane sulfonate by virtue of hydrolysis. But, inasmuch as thehydroxyl radical in this sulfonate is hydrophilic in nature, there areinstances where said sulfonate is considered rather unnecessary for thepurpose of obtaining a more useful oilsoluble surface active agent. Insuch a case, therefore, it suffices to check the formation of hydroxylradical by first subjecting sulfonic acids contained in the products ofsulfonation to neutralization with an alkali metal hydroxide andsubsequently adding a sultone cracking agent in such an amount asexceeding the equivalent subsequent to the ring-opening of the residualsultone.

As for the sultone ring opening agent to be employed for this purpose,such substances as alcohol, phenol, carboxylic acid, primary orsecondary amines, imines, the amide or imide of either carboxylic acidor sulfonic acid, active hydrogen-containing compounds such as mercaptanor thiourea or N-substitution products thereof, and those compounds notcontaining active hydrogen such as amine sulfonates, are suitable.Besides, the tertiary amine, thioether, t-phosphine, etc., are alsoapplicable. Of these sultone ring opening agents such a one as containsactive hydrogen is to be employed in the presence of a salt or a radicalcapable of bonding onto the sulfonic acid radical, and can have as asubstituent radical, an aliphatic radical, alicyclic radical, aromaticradical, etc., or a single or multifunctional radical. The salt for thispurpose can be the salt of an inorganic acid, thiocyanic acid,thiosulfuric acid or hydrogen sulfide. Meanwhile, such sultone ringopening agent as does not contain active hydrogen does not necessarilyrequire such salt or neutralizing agent.

What is especially noteworthy with respect to the neutralization processunder the present invention is the fact that, notwithstanding the highmolecular weight thereof, the viscosity of the olefin sulfonic acidaccording to the present invention is about 1000 cp at 50C at themaximum, and therefore, even when the present olefin sulfonic acid isquickly added to a basic aqueous solution for neutralization andstirred, it never gives rise to the so-called solid matters, but it isreadily neutralized usually without employing any solvent. Thissolidifcation is feasible in the process of neutralization on theoccasion of preparing a water-soluble surface active agent even in casewhere an oz-olefin sulfonate having the chain length in the range of C Cis employed. In this case, however, unless either the temperature ismaintained as high as more than C or an appropriate solvent is added,the neutralization will not progress. In case of the present invention,too, some quantity of solvent, if deemed necessary, can be employed inthe process of neutralization.

A slurry thus obtained and containing the alkali or I sultone crackingagent is subsequently maintained at a fixed temperature for a fixedperiod of time while being stirred, thereby affecting hydrolysis or ringopening of the sultone. The temperature and the time for suchdecomposition are closely related to each other; namely, the higher thetemperature, the shorter the time required. The requirements for thedecomposition of sultone in terms of temperature and time are l00-200Cand 7 hours-l minutes, respectively. When these requirements are met,the ring opening of sultone is readily effected.

In this connection, it goes without saying that it is necessary tomaintain said slurry to be alkaline by controlling the amount of thealkali or sultone ring opening agent.

In case of a sultone thus decomposed, it is next subjected to theafter-treatment as set forth below: the product resulting from thedecomposition of the sultone usually contains mixed therein unreactedoil, water, some inorganic salt, alkali, etc., in addition to olefinsulfonate, so that this product is serviceable, in that condition, as anoil-soluble surface active agent, but

there are many instances where the effective components (inclusive ofthe unreacted oil) thereof are to be singled out for use, andaccordingly, it is necessary to eliminate therefrom such impurities asinorganic salt, water, etc. As the means for separating said impuritiesfrom the effective components of the product from the decomposition, apetroleum based solvent or a chlorinated hydro-carbon based solvent isemployed. That is, the effective components consisting substantially ofolefin sulfonate are readily soluble in said solvents and can be therebyextracted, while the impurities remain as a residue. The petroleum basedsolvents suitable for this purpose include pentane, hexane, ligroin,octane, gasoline, kerosene, etc., while the chlorinated hydrocarbonbased solvents suitable for the same include trichloroethylene,tetrachloroethylene, carbon tetrachloride, etc. Further, in case wheresimultaneous separation of polysulfonates is intended, a lower alcoholbased solvent, such as ethanol, isopropanol, etc., may be additionallyemployed. Upon effecting the extraction, by evaporating the solventunder atmospheric pressure or at a reduced pressure, an olefin sulfonatehaving a high molecular weight and containing unreacted oil can beobtained. In this connection, said olefin sulfonate suffers nodeterioration of its own efficiency because it contains the unreactedoil to a degree, and, accordingly, there is no necessity to go to thetrouble of separating said unreacted oil by means of extractionemploying an additional solvent, distribution, absorption, or the like;on the contrary, such unreacted oil can be rather positively made to becontained in the olefin sulfonate for the purpose of reducing itsviscosity.

The oil-soluble surface active agent, which consists substantially ofthe olefin sulfonate according to the present invention, is rich insulfonate and superior in color tone, anticorrosive property,oil-solubility, etc., as compared with the conventional salt of mahoganyacid and the like, and has such merits that it is very easy to workbecause of the low viscosity thereof and renders it possible to produceoptionally products having almost uniform properties. And, from theviewpoint of the efficiency, the present surface active agent, whencompared with conventional salt of mahogany acid and the like, hasproved capable of demonstrating superior lubricating effect,anti-corrosive property, emulsifying effect, hydrating effect asrequired of a dry-cleaning detergent, and so forth.

Hereunder given is a further elucidation of the present invention byreference to specific examples.

DESCRIPTION OF THE PREFERRED EMBODIMENTS EXAMPLE 1 3000g of a-olefinhaving 16 carbon atoms (composed of 93 percent of a-olefin, 6.6 percentof vinylidene type olefin and paraffin and 0.4 percent of inner olefin)prepared through ethylene polymerization and 600g of nickel oxidecatalyst (composed of 6.2 percent of NiO, 84.4 percent of SiO and 9.4percent of Al O were put in a 4 necked flask and caused to react for 8hours at 35C in the presence of N current while being stirredvigorously. After filtering away the catalyst, the unreacted olefin(mostly isomerized inner olefin) was evaporated under a reducedpressure, whereby a dimerized olefin (including some higher polymerizedolefin) was obtained at a 50 percent yield.

The result of analysis by spectra of infrared rays of thus obtaineddimerized olefin showed almost no double bond at the end of 910', butthere was observed, at 965*, a peak ascribable to a trans-form innerdouble bond, and another peak-though weak and indistinctat 800-900. Thisfact verifies that the present olefin contains a substantial amount ofcomponents having three substituents and double bond. This highmolecularolefin mixture was sulfonated by employing an apparatus for use incontinuous thin-film sulfonation, sized for laboratory use.

This reaction apparatus is made of Pyrex glass, provided with a reactor5mm in diameter and 120mm in length, and so devised as to make theolefin and 50:, gas flow down in a parallel fashion to come into contactwith each other. As for the conditions for reaction, the temperature ofS0 gas was 50C, the concentration of was 2.8 percent by volume (asdiluted with nitrogen gas), the time for contact was 30 seconds, therate of olefin feed was 6g/min, and the temperature of the olefin was25C. In this context, the mol ratio of S0 [olefin and the reactiontemperature employed were as shown in Table-l appearing in thefollowing.

A variety of sulfonic acids prepared as above were respectivelyneutralized with a 10 percent aqueous solution of NaOH in such an amountas to be equal in moles to the S0 introduced at the time of sulfonation,and then subjected to hydrolysis of the sultone at 160C for 20 minutes,thereby obtaining the sodium salt of the olefin sulfonic acid.

This sodium salt of the olefin sulfonic acid, when mixed with ethanoland subjected to extraction processing by employing petroleum ether,divided into two layers: the upper layer, namely, the petroleum etherlayer, was composed of the olefin sulfonate and unreacted olefinextracted thereby, while the lower layer consisted of water and ethanol.By removing the solvent from said petroleum ether layer, there wasobtained the olefin sulfonate of the present invention. A single workingof this extraction processing suffices to eliminate almost completelythe surplus alkali and Glaubers salt, producing a product with a lightcolor and low viscosity. The loss of the olefin sulfonate mixture in thecourse of refining work was always less than 3 percent.

Table 1 Relationship of M01 Ratio of SO /High Molecular Weight Olefin (Creaction Temperature and Properties of the Olefin Sulfonate Produced No.Mol ratio Temperature Percent Color Solubility 3) of 80 forsulfonconvertone high moleation reac sion of 2) CCl, tetrapetroleumbased spindle cular weight tion (C) reaction (Klett chlorodry-cleaningoil olefin 1) value) ethylene solvent No. l

Table l-Continued Relationship of M01 Ratio of SO /High Molecular WeightOlefin (C reaction Temperature and Properties of the Olefin SulfonateProduced No. Mol ratio Temperature Percent Color Solubility 3) of S forsulfonconvertone high mole ation reacsion of 2) CCl tetrapetroleum basedspindle cular weight tion (C) reaction (Klett chlorodry-cleaning oilolefin 1) (7c) value) ethylene solvent No. l

6 9O 92 9O 0 0 0 0 7 1.5 50 95 1 10 0 O 0 0 Remarks:

1) Method of analysis: Estimated by sulfur content in the high molecularolefin sulfonate.

2) The Klett value in case of 57z-isooctane solution. 3) In case of 30Wt7z solution at 25C; the mark 0 denotes good.

The sulfonate (Na salt) obtained through the sulfonation under thecondition of the mol ratio of SO /high molecular olefin being 1.0 andthe reaction temperature being 50C as appearing in the foregoingTable-1,

was employed as an anionic surface active agent of the active ingredientdry-cleaning detergent in lieu of conventional sodium salt of mahoganyacid. The content of the olefin sulfonate (Na salt) within thedry-cleaning detergent in the present example was in the range of 5-30percent. The present olefin sulfonates, both the one for use inpetroleum-based solvent and that for use in tetrachloroethylene-basedsolvent, have proved to stand comparison with conventional products inevery respect, such as cleansing efficiency, hydrating efficiency,finishing effect, softness of the finish, odor, influence on the fiber,etc., and therefore, was capable of serving equally well.

Especially, in the case of the olefin sulfonate employing mahogany acidNa according to the present invention, its hydrating property is by farsuperior to the conventional ones in that it can be solubilized with oneand a half times as much water.

Further, the viscosity of the present sodium salt of olefin sulfonatewas as shown in the following:

No.2 300 cp (25C) No.3 450 cp( No.7 600 cp( mahogany acid (sodium salt)3000 cp EXAMPLE 2 A material composed of 1 part by weight of a-olefinhaving a carbon atom number in the range of -18 which was obtainedthrough wax-cracking and 1 part by weight of a-olefin having 18 carbonatoms which was obtained through ethylene polymerization was mixed with5 percent of B1 etherate (BF contentfl6 percent) and subjected todimerization at 120C for 6 hours, whereby an olefin having a carbon atomnumber in the range of 33-56 was obtained at a yield of 80 percent.Subsequently, the thus prepared material olefin was introduced into theindustrial-size sulfonation apparatus disclosed in the Japanese PatentGazette Sho- 42-252, and subjected to sulfonation by applying sulfuricanhydride (mole ratio of SO /material olefin=l.15) diluted with dry airand at the reaction temperature of 30 C and C respectively, wherebythere were obtained two types of products from the sulfonation reactionat the rate of 100 kg/hr each. The contact time on this occasion was 25seconds on the average.

The apparatus employed in the present example is provided with al20'"-long main reaction zone, which is further equipped with athermometer at 3 places, viz. the upper, middle and lower part thereof,respectively.

The reaction products (acids) obtained as above were neutralizedrespectively with a 10 percent aqueous solution of NaOH in such anamount as equivalent to percent of S0 introduced at the time of thesulfonation reaction, and then subjected to hydrolysis of the sultone atthe temperature of 150C for 45 minutes.

Subsequently, by refining the above olefin sulfonates through the sameprocess as in Example 1, highmolecular weight oil-soluble surface activeagents were prepared. The properties of these agents are as shown in thefollowing Table-3, which verifies that it is possible to provide, on anindustrial basis, a sulfonate of the same quality as that prepared onthe laboratory scale.

Table 2 Properties of C Olefin Sulfonate Prepared on Industrial ScaleSample Tempera- Percent Color Solubility ture for conver- Tonesulfonasion of (Klett CCl, tetrapetroleumspindle tion rereaction value)chlorobased dryoil action ethylene cleaning No. 1

( solvent Sample -l 50 91.5 80 0 0 0 0 Sample The symbol 0" denotesgood.

Sample-l was subjected to double decomposition to Further, thesulfonation of the foregoing olefins by reduce it to Ca salt anddissolve it in spindle oil No. 1. means of S continuous processing isalways readily The efficiency of the thus prepared additive forlubriperformed except for the case of a-olefin having 20 cant wascompared with that of Ca salt of mahogany carbon atoms, and theneutralization and hydrolysis are acid. The result was as shown in thefollowing Table-3. also easy to perform.

Table 3 Anti-corrosive property test Sample Wet strength" Corrosion ofCoefficient Baking" (non-rust steel sheet of friction Load period (hr))(kg/cm spindle oil No.

1 only 1 0.304 2.5 spindle oil No.

Ca salt of mahoacid 3% 48 2 0.223 3 spindle oil No.

Ca salt of mahoof sulfonate under Example Remarks:

According to JlS-Z-O223, .llS-Z-29 l 2.

"According to JlS-K- l 3 "Result of test by means of Soda'spendulum-type oiliness tester (25C; 65% RH). "According to .llS-K-25 l9.

Further, for the purpose of comparison, the solubility In the case ofsaid a-olefin having 20 carbon atoms, of various olefin sulfonates inthe range of C to C for the melting point is 29C, and it is necessary totreat it various solvents will be shown in the following Table-4. byheating.

Besides, the comparative difficulty in preparation and the Solubilityfor solvent of the Product under p Moreover, it is apt to give rise toclots at the time of invention will be Shown in the following Table-5 yneutralization, and therefore, it is necessary either to means ofcomparing -olefin having Carbon atoms in heat it up to a hightemperature or to use some solvent the range of 32 to 40 with mahoganyacid salt. 40 j i tl Table 4 Solubility of C1541 Olefin Sulfonates forVarious Solvents (Na salt) Solubility for various solvents (In case of30% solution at 25C) Olefin No. of Water EtOH BuOH Petro- Paraffin-Spindle Petroleum- Tetrachloro- Carbon leum based oil based dryethyleneAtoms ether lubricant Nov 1 cleaning Alkyl solvent Radical a-ole-Straight fin Chain C 0 O A x x x x x C A o o x x x x X Vinylidene- C o oA X x X x x type olefin C A o o A A A A A Dimerized olefin C o o A x x xx x C A o o A A A A A Trimerized olefin C o o A x x x x x C A o o A A AA A Remarks:

mark x denotes insoluble mark A denotes partially soluble mark 0 denotestransparent and soluble.

Comparative Difficulty in Preparation of Cagqo Olefin Sulfonates andSolubility Thereof for Various Solvents Material Alkyl Radical No. SaltDifficulty in Difficulty in of Carbon Atoms Sulfonation after-treatmentHeating of material Neutralization is rather C Na or dilution of 501-difficult; heating up to vent is required high temperature and dilu- CCa tion of solvent is required a-olefin C Na C32 Na H 1! C36 Na I, H C40Na 1, 1, Example 1 C 50;, mol ratio 1.00, Reaction Examples temperature50C Na good good of Present Invention Example 2 C Na good good Olefin Smol ratio 1.15 Reaction Temperature 50C, 80C Ca good good Mahogany C HSO Na Na Extraction and refining is Acid required Salt C l'l so /Ca CaSolubility for various solvents (in case of solution at 25C) Water BuOHPetroleum ether Spindle oil Paraffin-based CCl Tetrachloro No. 1lubricant ethylene A o A A A A A x A A A A A A x A A A A A A x A A A A AA x A A A A A A x A A A A A A x A o o o o o x A o o o o o x A o o o o 0x 0 o o A o o x A o o o o 0 Remark: Mark x denotes inso1uble" Mark Adenotes partially soluble" and Mark 0 denotes transparent and soluble,

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

l. A low viscosity, oil-soluble surface active agent prepared bysulfonating monoolefin of the formula 1.5/1.0, at a reaction temperaturefrom 5 to C above the solidifying point of said olefin, to form asulfonated reaction product, containing alkenesulfonic acids andsultones,

and neutralizing said reaction product by adding to said reactionproduct from 0.6 to 1.0 equivalents, based on the S0 reacted, of analkali metal, ammonium or alkaline earth metal hydroxide or carbonate,the amount added being sufficient to render the reaction mixturealkaline and then maintaining said reaction mixture at a temperature of100 to 200C for a period of 1 minute to 7 hours to hydrolyze thesultones.

2. A surface active agent as claimed in claim 1, in which saidmonoolefin is a dimerized monoolefin prepared by dimerizing astraight-chain a-olefin having 16 to 20 carbon atoms.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 883583 Dated y 1975 Inventor (s) Masuzo Nagayama and Hiroshi Okada It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

On the first page insert the following:

--Foreign Application Priority Data July 1, 1969 Japan 44-51 929 Signedand Scaled this twenty-sixth Day Of August 1975 [SEAL] A ties r.-

RUTH C. MASON C. MARSHALL DANN Arresting Officer (ommissinm'r uj'laientsand Trademarks

1. A LOW VISCOSITY, OIL-SOLUBLE SURFACE ACTIVE AGENT PREPARED BYSULFONATING MONOOLEFIN OF THE FORMULA
 2. A surface active agent asclaimed in claim 1, in which said monoolefin is a dimerized monoolefinprepared by dimerizing a straight-chain Alpha -olefin having 16 to 20carbon atoms.